Conductive polymer composite structure

ABSTRACT

In order to obtain actuator elements capable of being displaced such as expansion and contract or bending for practical use even when used as actuator elements with larger size, stacked layers or bundles in which conductive polymer-containing layers or fiber-like tubes are provided with conductive polymer composite structures which include conductive substrates and conductive polymers, said conductive substrates have deformation property, and conductivity of said conductive substrates is not less than 1.0×10 3  S/cm are used.

FIELD OF THE INVENTION

The present invention relates to conductive polymer composite structuresin which conductive polymers and conductive substrate are composite,process for producing the same, process for producing conductivepolymers, bundles and stacked layers of conductive polymer compositestructures.

BACKGROUND ART

Conductive polymers such as polypyrrole and the like are known to haveelectrochemomechanical deformation, phenomena of expansion andcontraction by electrochemical redox reaction. Recently, thiselectrochemomechanical deformation of conductive polymers has beenattracting public attention, because this is expected to be applied forthe use of artificial muscles, robot arms, artificial arms, actuatorsand the like and applications not only for smaller equipments such asfor micro machines and the like, but also for larger machines have beenattracting public attention as well.

As a process for producing conductive polymers, a process byelectrochemical polymerization method is common. A commonelectrochemical polymerization method includes by adding monomercomponents such as pyrrole and the like in electrolytic solution,providing a working electrode and a counter electrode in thiselectrolyte, and applying voltage between the electrodes, therebyforming conductive polymers as films on the working electrode (e.g. seepages 70 to 73, “Conductive polymers” 8^(th) edition by Naoya Ogata,published by Scientific K. K, Feb. 10, 1990”). Conductive polymersobtained by electrochemical polymerization can be subject todisplacement such as expansion-contraction or bending by applyingvoltage to conductive polymers formed like films.

When elements which include conductive polymers manufactured byelectrochemical polymerization (hereinafter called conductive polymerelements) are used as actuators in a driving part for uses of largesized equipments such as robot arms of industrial robots and the like,and artificial muscles such as artificial hands and the like, comparedwith elements for the uses of small sized actuators such as for micromachines and the like, it is necessary to make sizes of elements largeenough to obtain larger amount of expansion-contraction or largerelectrochemical stress. Therefore, in order to enlarge sizes ofconductive polymer elements, it is necessary that conductive polymerfilms obtained by electrochemical polymerization are processed to belonger or thicker by piling up plural of films, or the like.

As conductive polymer elements with larger sizes, with a view toobtaining larger expansion and contraction in the length direction andin the height direction compared with conventional uses, longerconductive polymer elements compared with conventional conductivepolymer elements are also used since they are sometimes used as drivingparts, the use which requires enlarged conductive polymer elements inthe length direction or in the height direction. Desirableelectrochemical strain can be obtained by selecting the kinds ofconductive polymers and dopants depending on the, uses and bycontrolling the length of conductive polymer elements since deformationratio of conductive polymer elements is determined by the kinds ofconductive polymers and dopants which are included in conductive polymerelements.

However, in obtaining large electrochemical strain, there is a problemthat, regarding the conductive polymer elements with selected kinds ofconductive polymers and dopants, for example, satisfactory potentialcannot be applied at the upper portion of elements since theconductivity of conductive polymers obtained by electrochemicalpolymerization is generally around 10² S/cm even when electrodes areprovided on the whole bottom surface in the case where the conductivepolymer elements enlarged in the direction of the columnar body heightare used, and in the dedoped state, since conductivity further lowers,satisfactory potential cannot be applied at the upper portion ofelectrodes and when electrodes such as metal plates and the like areprovided in the height direction, electrodes such as metal plates andthe like inhibit the motion of conductive polymer elements, causing theproblem of difficulty for said conductive polymer elements to expand andcontract.

In order to solve the above problem, as a means to obtain largeelectrochemical strain of conductive polymer elements, one idea ofpasting highly conductive metal films on surfaces of conductive polymerelements may be considered. However, since conductive polymer elementsprovided with said metal films on surfaces inhibit deformation sincehighly conductive metal films have little deformation property and thesefilms cannot be applied to actuators which move in a linear manner byvoltage application because displacement by electrochemical redoxbecomes bending but not expansion and contract. In addition, whenconductive polymer elements provided with said metal films are appliedto actuators which moves in a linear manner, a problem that metal filmsare separated from metal films due to repeated displacement and whenmetal films are firmly fixed to conductive polymer elements toconductive polymer elements with adhesives and the like, the problemthat even bending motion is inhibited occurs. In addition, elementscapable of uniformly applying electric charge over a whole element byconnecting a lead to one point of a bottom surface of said elements aremore advantageous since a composition of a element-driving device is notrestricted.

Further, since large sized conductive polymer elements do not have highmechanical strength in conductive polymer elements, mechanical strengthrequired for applications to robot arms such as industrial robots andthe like, artificial muscles such as artificial hands which are theapplications to large sizes may be not enough. Therefore, it isdesirable to employ reinforcement means which improves mechanicalstrength of conductive polymer elements when large sized conductivepolymer elements are used as practical uses.

Further, since conductive polymers are liable to be cut during theoperation process because mechanical strength of conductive polymersthemselves is not high, it is difficult to form desirable conductivepolymer electrodes, that is, with an external diameter or width of lessthan 1 mm by processing such as cutting conductive polymer filmsobtained by electrochemical polymerization and the like in order toobtain small-sized conductive polymer elements represented by micromachines such as nano machines, catheters and the like. In addition,since conductive polymer elements are hard to be melted, productionmethods such as extrusion moldings, injection moldings and the likecannot be employed, the methods usually employed in producing thin linessuch as wires or cylindrical resin mold products. For this reason,actuator elements which are driven to make expanding and contractingmotion or to make bending motion by electrochemomechanical deformationof conductive polymers are not put into practical uses as small sizeddriving parts which include nano machines and micro machines. Therefore,in order to use for small sized elements represented by nano machinesand micro machines, it is also desirable to obtain actuator elementswhich are driven to make expanding and contracting motion or to makebending motion by electrochemomechanical deformation of conductivepolymers as small sized elements with external diameter or width of lessthan 1 mm.

In addition, since it is desirable that large sized actuator elementscan produce uniform electrochemical stress in each portion of saidactuator elements, it is desirable to uniformize amount of conductivepolymers regarding each portion of actuator elements as a whole.Therefore, it is desirable to make further large actuator elements byusing plural of actuator elements capable of being displaced forpractical use such as expansion and contract or bending. It is necessarythat each of plural actuator elements which compose one large sizedactuator is obtained but it is desirable that a number of them areproduced efficiently and easily in a short time.

It is the object of the present invention to provide elements capable ofbeing displaced for practical use such as expansion and contract orbending even when conductive polymer elements are used as large sizedactuator elements.

SUMMARY OF THE INVENTION

The present invention relates to conductive polymer composite structurescomprising conductive substrates and conductive polymers, wherein saidconductive substrates have deformation property and conductivity of saidconductive substrates is not less than 1.0×10³ S/cm. By using saidconductive polymer composite structures, deformation property is goodeven when the conductive polymer composite structures are used as largersized actuator elements. Since said conductive polymer compositestructures are provided with structures capable of applying potential towhole elements even when they are used as conductive polymer elementselongated in size in the length direction and in height direction,satisfactory voltage can be applied for driving end portions when usedas actuators.

In addition, since the present invention relates to a process forproducing conductive polymer composite structures in which electrodeholders which can be immersed in an electrolytic bath are immersed inelectrolytic solution and then conductive polymers and conductivesubstrates are combined by electrochemical polymerization interposingelectrolyte between a counter electrode and a working electrode andsince the present invention relates to a process for producingconductive polymer composite structures in which said working electrodeholders are provided with working electrodes, working electrode terminalportions, and electrode holder portions and in which said workingelectrodes are attached to said working electrode terminal portions, andsaid working electrodes include at least coiled conductive substrates.In said production process, since electrochemical polymerization isconducted in a state where counter electrodes are put in the vicinity ofworking electrodes, a large number of conductive polymer compositestructures can easily be obtained for short times at the same time.

In addition, the present invention also relates to a process forproducing conductive polymer composite structures in which bundles inwhich coiled conductive substrates are bundled are used as said workingelectrodes.

When conductive substrates which are said working electrodes are coiled,resistance gets large since metal wires are thin and long, and thelarger the conductive substrates get, the less potential transmissionbecomes, causing the problem of difficulty in forming conductivepolymers on the conductive substrates. By this producing process, suchproblems can be solved.

BRIEF DESCRIPTION OF THE DRAWINGS

The preferred embodiments of the present invention are shown by way ofexample, and not limitation, in the accompanying figures, in which:

FIG. 1 is a typical perspective view of conductive polymer compositestructures of the present invention when spring-type members are used asconductive substrates.

FIG. 2 is a partial enlarged view of a longitudinal section ofconductive polymer composite structures in FIG. 1.

FIG. 3 is a typical perspective view of conductive polymer compositestructures of the present invention when metal meshes are used asconductive substrates.

FIG. 4 is a typical perspective view of conductive polymer compositestructures of the present invention when tube-like conductive substratesare fixed in parallel to conductive substrates in a stretchable way.

FIG. 5 is a perspective view of cylindrical conductive polymer compositestructures using coiled metal spring-type members as conductivesubstrates.

FIG. 6 is a partial enlarged perspective view of one end of groups ofbundles of cylindrical conductive polymer composite structures.

FIG. 7 is a partial enlarged perspective view of one end of groups ofbundles of cylindrical conductive polymer composite structures.

FIG. 8 is a partial enlarged perspective view of one end of groups ofbundles of cylindrical conductive polymer composite structures.

FIG. 9 is a perspective view showing one embodiment of driving member 23of actuators using bundles of conductive polymer composite structures.

FIG. 10 is a front view of an electrode holder in the producing processof the present invention.

FIG. 11 is a typical perspective view showing the state in which a leadis connected to an electrode holder in the producing process of thepresent invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(Conductive Polymer Composite Structures)

Conductive polymer composite structures of the present invention areconductive polymer composite structures comprising conductive substratesand conductive polymers, wherein said conductive substrates havedeformation property, and conductivity of said conductive substrates isnot less than 1.0×10³ S/cm.

Hereinafter, shapes of conductive polymer composite structures of thepresent invention and forms in which conductive substrates are includedin the conductive polymer composite structures of the present inventionare explained by using drawings, however, shapes of conductive polymercomposite structures and forms in which conductive substrates areincluded in the conductive polymer composite structures of the presentinvention are not limited to what are illustrated in these drawings aslong as conductive polymer composite structures can obtain satisfactorydisplacement such as expansion and contraction or bending as practicalperformances.

FIG. 1 is a, typical perspective view of conductive polymer compositestructures of the present invention when coiled metal spring-typemembers are used as conductive, substrates. FIG. 2 is a partial enlargedview of a longitudinal section of conductive polymer compositestructures in FIG. 1. In conductive polymer composite structure 1 inFIG. 1, coiled metal spring-type member 3 is used as a conductivesubstrate. As shown in FIG. 2, in cylindrical conductive polymercomposite structure 1 in FIG. 1, spaces between wires which composecoiled metal spring-type members are fined by conductive polymer 2, andconductive polymer 2 and conductive substrate 3 are completed. By thiscomposition, even when the size of actuators are made large, conductivepolymer composite structures can produce satisfactory displacement suchas expansion and contraction or bending as practical performances. Inaddition, since conductive polymer composite structures in FIG. 1include coiled metal spring-type members, wires of metal spring-typemembers can function as reinforcement materials when external force isapplied from the direction vertical to an outer surface, improvement inmechanical strength can also be attained.

FIG. 3 is a typical perspective view of conductive polymer compositestructures of the present invention when metal meshes which are networkmembers are used as conductive substrates. In cylindrical conductivepolymer composite structure 4 in FIG. 3, spaces between wires whichcompose metal mesh are filled and conductive polymer 5 and conductivesubstrate 6 are completed. By this composition, even when the size ofactuators are made large, conductive polymer composite structures canproduce satisfactory displacement such as expansion and contraction orbending as practical performances. In addition, since conductive polymercomposite structures in FIG. 3 include metal mesh, wires of metalsspring-type members can function as reinforcement materials whenexternal force such as tension and the like is applied, improvement inmechanical strength can also be attained.

Although said conductive polymer substrates have space portions as shownin FIGS. 1 and 3 between conductive wires which compose coiled metalspring-type members and metal mesh, said space portions are notspecifically limited. When spaces between wires are large and thereforesaid space portions are large, by combining auxiliary electrodesubstrates with said conductive substrates, conductive polymer compositestructures to in which space portions are filled by conductive polymerscan be obtained. For example, when conductive substrates are metalmeshes with large openings, metal plates are used as auxiliary electrodesubstrates, and by applying electrochemical polymerization using saidmetal meshes laminated on said metal plates as working electrodes,followed by removing said metal plates, conductive polymer compositestructures in which metal mesh space portions are filled by conductivepolymers can be obtained. In addition, said conductive polymersubstrates may be provided with space portions which are other thanwires, such as leaf springs and the like.

Said conductive substrates may be included in such a way thatsatisfactory potential is applied over said whole conductive polymercomposite structures, and as shown in FIGS. 1 and 3, said conductivesubstrates may be arranged in the vicinity of a center of conductivepolymer composite structures in the thickness direction or saidconductive substrates may be arranged in the vicinity of surfaces ofconductive polymer composite structures, however, it is preferable thatsaid conductive substrates may be arranged in the vicinity of a centerof conductive polymer composite structures in the thickness directionsince satisfactory potential can be easily applied to the wholeelements. In addition, it is preferable that said conductive substratesare included in substantially whole said conductive polymer compositestructures since, satisfactory potential can be easily applied to thewhole elements, and it is preferable that said conductive substrateshave the same shapes as those of said conductive polymer compositestructures since satisfactory potential can be easily applied to thewhole elements.

Shapes of said conductive polymer composite structures are notspecifically limited and as desired, they may be prepared in columnarshapes, prismatic shapes, plate shapes, sheet shapes, tubular shapes,cylindrical shapes, and the like. For example, said conductive polymercomposite structures may be cylindrical shapes as shown in FIG. 1 orsaid conductive polymer composite structures may be film-like shapes asshown in FIG. 3.

In addition, said conductive polymer composite structures may beprocessed to make them desired shapes as required when the size ofelements is large and when the process can easily be made. For example,columnar conductive polymer composite structures may be obtained bywinding film-like conductive polymer composite structures shown in FIG.3 and by filling conductive polymers in communicating space portions incylindrical shaped conductive polymer composite structures of FIG. 1.

Further, as shown in FIG. 4, coiled metal spring-type members may beprepared in the form of an expander, thereby compounding alignedconductive substrates fixed in parallel in a stretchable way withconductive polymers, or conductive polymer composite structures withmetal meshes may be laminated. In addition, depending on uses, desiredprocess may be applied.

Further, in conductive polymer composite structures of the presentinvention, groups of conductive polymer composite structures can beformed by forming bundles of a plural of conductive polymer compositestructures which use coiled metal spring-type members as conductivesubstrates further followed by bundling the conductive polymer compositestructures. FIG. 5 is a drawing of cylindrical conductive polymercomposite structures using coiled metal spring-type members asconductive substrates. FIG. 6 is a partial enlarged perspective view ofone end regarding bundles (the first bundles of conductive polymercomposite structures) of columnar conductive polymer compositestructures obtained by bundling cylindrical conductive polymer compositestructures shown in FIG. 5. FIG. 7 is a partial enlarged perspectiveview of one end regarding groups of bundles (the second bundles ofconductive polymer composite structures) of columnar conductive polymercomposite structures obtained by bundling the first bundles ofconductive polymer composite structures shown in FIG. 6. FIG. 8 is apartial enlarged perspective view of one end regarding bundles of groups(the third bundles of conductive polymer composite structures) ofconductive polymer composite structures obtained by bundling the groupsof cylindrical conductive polymer composite structures shown in FIG. 7.

In FIG. 5, conductive polymer composite structures 12 are tubularconductive polymer composite structures obtained by jointing metal wires13 or 13′ at both ends of coiled metal spring-type members in the lengthdirection as a conductive substrate, connecting said metal wires 13 and13′ to a power supply and generating conductive polymers on a conductivesubstrate by a publicly known electrochemical polymerization method. InFIG. 5, although conductive polymer composite structures 12 are providedwith metal wires on both ends, the metal wire may be provided on eitherend thereof.

In FIG. 6, bundles 14 of conductive polymer composite structures are thefirst bundles of conductive polymer composite structures obtained bybundling conductive polymer composite structures 12. By making bundlesof conductive polymer composite structures, when they are driven asactuators, larger electrochemical stress can be obtained compared withconductive polymer composite structures. Methods of bundling conductivepolymer composite structures to obtain bundles of conductive polymercomposite structures are not specifically limited as long as they arethe methods of bundling publicly known linear object. In the embodimentin FIG. 6, metal wires 13 provided at the end of conductive polymercomposite structures 12 are bundled to form a bundle of metal wires 15.Methods of fixing a bundle of metal wires in a state where the metalsare bundled are not specifically limited and such methods may includeforming coated films with adhesives and the like around the outerperiphery of a bundle of metal wires or fixing a state where the metalsare bundled by wrenching metal wires. In addition, in order to easilyform a state where conductive polymer composite structures are bundled,it is preferable that bundles of conductive polymer composite structuresare provided with a bundle of metal wires in which conductive polymercomposite structures are fixed with metal wires on both ends ofconductive polymer composite structures bundled on both ends. Further,when applying voltage to conductive polymer composite structures to makebundles of conductive polymer composite structures actuators, potentialmay be applied either to metal wires of both ends of conductive polymercomposite structures or to one end thereof.

In FIG. 7, groups of conductive polymer composite structures 16 are thesecond bundles of conductive polymer composite structures obtained bybundling bundles 14 of conductive polymer composite structures. By beinggroups of bundles of conductive polymer composite structures, whendriven as actuators, the groups of bundles of conductive polymercomposite structures can obtain larger electrochemical stress comparedwith bundles of conductive polymer composite structures.

Methods of bundling bundles of conductive polymer composite structuresto produce groups of bundles of conductive polymer composite structuresare not specifically limited as long as they are the methods of bundlingpublicly known linear objects. In addition, in FIG. 7, by bundling metalwire bundles 15 provided in bundles 14 of conductive polymer compositestructures, metal wire bundle groups 17 are formed. Methods of fixinggroups of metal wire bundles in a state where metal wire bundles arebundled are not specifically limited and such methods may includeforming coated turns with adhesives and the like around the outerperiphery of a group of metal wire bundles or fixing a state where themetal wire bundles are bundled by wrenching metal wire bundles to form agroup.

In FIG. 8, groups of bundles 16 of seven conductive polymer compositestructures are further bundled, thereby forming bundles 18 of groups ofconductive polymer composite structures. By being groups of conductivepolymer composite structures, when driven as actuators, by combininggroups of bundles of conductive polymer composite structures depending,on required electrochemical stress, desired electrochemical stress canbe obtained.

FIG. 9 shows one embodiment of driving members 23 of actuators usingsaid bundles of conductive polymer composite structures. Bundles 19 offour conductive polymer composite structures are fitted in poresprovided with fixing members 20 and 20′ and are fixed by adhesives andthe like. Metal wires provided in bundles of four conductive polymercomposite structures form metal wire groups 21 in a bundle, and areconnected to a power source interposing a lead. In catching portion 22provided in fixing member 20′, wires and the like positioned inoperating objects are connected. Actuators can be formed by impregnatingdriving members 23 in electrolytic solution, and by coating solidelectrolytes and driving members with resins and the like by placingsolid electrolytes in a way to make them contact with bundles ofconductive polymer composite structures.

By applying voltage to conductive polymer composite structures,conductive polymer composite structures deform and wires and the likeconnected to catching portions 22 are pulled, thereby making objectsmove.

In FIG. 9, four of said bundles are positioned in parallel. However,bundles used as driving members of actuators are not specificallylimited in numbers used and depending on required electrochemicalstress, not less than 100-unit bundle such as about 1000-unit bundle canbe used.

In order to use for actuators which are used as large-sized drivingdevices, it is preferable to use not less than 100-unit bundle forobtaining large electrochemical stress. Regarding alignment of saidbundles, tubular cylindrical and prismatic shapes may be formed, and forexample, tubular can be formed by arranging about 600-unit conductivepolymer-metal wire composites. In addition, said fixing members can showeffect of bundling composites by fixing apposition of conductivepolymer-metal wire composites and by fixing conductive polymer compositestructures to said fixing members.

(Conductive Substrates)

Conductive substrates included in conductive polymer compositestructures of the present invention have deformation property andconductive ratio of said conductive substrates is not less than 1.0×10³S/cm. Since said conductive substrates have its conductivity of not lessthan 1.0×10³ S/cm, even when the size of conductive polymer compositestructures which include said conductive substrates are made to belarge, displacement for practical use such as expansion and contract asactuators becomes available.

Materials of said conductive substrates are not specifically limited aslong as they show deformation property and have its conductivity of notless than 1.0×10³ s/cm. It is preferable that said materials are metals,metal plated polymer fibers, and carbon materials from the view point ofconductivity and mechanical strength. It is preferable that structuresof said conductive substrates are structures capable of extending andcontracting when conductive substrates have conductive property withconductivity of not less than 1.0×10³ S/cm by including non-deformationproperty materials such as metals and the like. Conductive substrates inwhich conductive substrates and conductive polymers are complexed, byhaving stretchable conductive substrates, displacement for practical usesuch as expansion and contract as actuators becomes available. Inaddition, said conductive polymer composite structures can have improvedmechanical strength since conductive substrates can function as corematerials in said conductive polymer composite structures.

Said stretchable structures are not specifically limited as long as theyare stretchable. Unlike plate structures or line segment structures, itis preferable that said stretchable structures have structures providedwith structures having space between members which compose conductivesubstrates such as coiled springs, plate springs, and meshes onlongitudinal section. As stretchable structures, spring-shaped members,meshed members, fiber structure sheets are exemplified as exemplars.

When said stretchable structures are spring-shaped members, they are notspecifically limited as long as they are stretchable and for example,rolled springs, plate springs, coiled springs can be used as conductivesubstrates.

When said stretchable structures are meshed members, they are notspecifically limited as long as they are stretchable and for example,meshed members in which meshed space portions are polygons such asquadrangles, hexagons, octagons and the like can be used. Although saidspaced portions are not specifically limited, when expansion andcontraction is liable to occur in only one direction due to the shapes,such conductive polymer composite structures can be obtained that cancontrol expansion and contraction in specific directions and whenexpansion and contraction is liable to occur in several directions suchas hexagons and the like due to the shapes, it is preferable to obtainsuch conductive polymer composite structures that can expand andcontract in other directions such as right to left or up and down andthe like.

Said meshed members may be the meshed members with a single layerprovided with meshed spaced portions represented by metal meshes or theymay be the meshed members in which plural of layers provided with meshedspaced portions are stacked. When said spaced portions are hexagons,said meshed members may be honeycomb structures in which spaces areformed in honeycomb.

Further, as said stretchable structures, they may be stretchable fiberstructure sheets. As said fiber structure sheets, they may be any one ofknitted works, textiles, and non woven cloths and deformation propertycan be shown depending on sheet structures, yarn characteristics, andyarn structures, however, plain stitches, circular rib stitches, andpurl stitches with good deformation property or fiber structure sheetsof knitted fabrics by weft knit composed of combinations thereof arepreferable since deformation property can easily be obtained.

When the structures of said conductive substrates are spring members ormeshed members, conductive substrates may be formed by conductive metalsor core materials may be coated with conductive metals by plating andthe like. When said conductive substrates are fiber structure sheets, itis preferable that the fibers which make up fiber structure sheets arecoated with conductive metals by plating and the like.

Conductive property of conductive substrates included in conductivepolymers of the present invention may show conductivity of not less than1.0×10³ S/cm as conductive substrates and the substrates may be composedof conductive materials such as conductive metals, carbons, and the likeor surfaces of the substrates may be coated with conductive materialssuch as conductive metals, carbons, and the like. With the conductivityof not less than 1.0×10³ S/cm as said conductive substrates, even whenconductive polymer composite structures with enlarged size in the lengthdirection or height direction are used, sufficient potential fordisplacement such as expansion and contraction can be applied to thewhole element. As conductive substrates including conductive metal,metal alloys such as those of Ag, Ni, Ti, Au, Pt, W and the like orother alloys such as SUS and the like can be used. In particular, it ispreferable that said conductive substrates include a single substance ofmetals regarding the element of Pt, W, Ni, Ta and the like in order toobtain conductive polymers with a large expansion and contractionperformance, and among them, W alloys and Ni alloys are particularlypreferable.

(Conductive Polymers)

As conductive polymers included in conductive polymer compositestructures of the present invention, publicly known conductive polymerscan be used, which include polypyrrole, polythiophene, polyaniline,polyphenylene, and the like. In particular, it is preferable that saidconductive polymers are conductive polymers which include pyrroleand/or, pyrrole derivatives in molecular chains not only for stabilityas conductive polymers but also for excellent electrochemomechanicaldeformation. In addition, since said conductive polymers show excellentdeformation ratio per redox cycle in electrochemomechanical deformationand displacement ratio per specific time, it is preferable that saidconductive polymers include anions which includetrifluoromethanesulfonate ion and/or plural of fluorine atoms which bondto central atom as dopants.

(Stacked Layer Structures)

The present invention relates to layered structures which includeconductive polymer-containing layers and solid electrolyte layers, inwhich said conductive polymer-containing layers are provided withconductive polymer composite structures which include conductivesubstrates and conductive polymers, in which said conductive substrateshave deformation property and in which conductivity of said conductivesubstrates is not lens than 1.0×10³ S/cm. Since said stacked layersinclude said conductive polymer-containing layers and said solidelectrolyte layers, electrolytes in said solid electrolytes are providedin said conductive polymer-containing layers and even when not in liquidelectrolytic solution, displacement such as expansion and contract orbending as actuators can be made.

Although it is preferable that said conductive polymer-containing layersin said electrolytes and said solid electrolyte layers directly contactwith each other, other layers can be interposed therebetween as long aselectrolytes in said solid electrolytes can be made to move to saidconductive polymers. For example, in tubular conductive polymercomposite structures in FIG. 1, said cylindrical stacked layers may beformed by filling solid electrolytes in a communicated space portions.In addition, by winding the conductive polymer composite structures inFIG. 3 around the outer surfaces of cylindrical solid electrolytes,cylindrical stacked layers say be formed.

(Process for Producing Conductive Polymers)

The present invention relates to a process for producing conductivepolymers by electrochemical polymerization using conductive substratesas working electrodes in which said conductive substrates havedeformation property and the conductivity of said conductive substratesis not less than 1.0×10³ S/cm. By using process for producing conductivepolymers of the present invention, conductive polymers are polymerizedelectrochemically and conductive polymer composite structures can easilybe obtained provided with structures in which conductive substrates andconductive polymers are complexed.

In order to easily obtain desired shapes depending on uses, it ispreferable that conductive substrates having similar rough contourshapes are used as working electrodes.

For example, cylindrical conductive polymer composite structures caneasily be obtained by electrochemical polymerization and withoutconducting any process by using coiled metal spring-shaped members whoserough contour is cylindrical as conductive substrates.

In the process for producing conductive polymers of the presentinvention, when coiled spring-shaped members made of metals are used asworking electrodes at the time of electrochemical polymerization,cylindrical conductive polymer composite structures can be obtained asshown in FIG. 1. In electrochemical polymerization, by applying voltageto coiled spring-shaped members made of metals which are workingelectrodes, conductive polymers are polymerized on a wire surface andconductive polymers grow from surfaces of working electrodes. By thisgrowth, as shown in FIG. 2, spaces between wire materials which make upcoiled spring members made of metals are filled in and cylindricalconductive polymer composite structures shown in FIG. 1 can be obtained.

FIG. 3 shows conductive polymer composite structures in which metalmeshes are used as working electrodes at the time of electrochemicalpolymerization in the process for producing conductive polymers of thepresent invention. In electrochemical polymerization, by applyingpotential to metal meshes which are working electrodes, conductivepolymers are obtained on a wire material surface of metal meshes andconductive polymers grow. By this growth, like when coiled springs areused as working electrodes, spaces between wire materials which make upmetal meshes are filled in and plate like conductive polymer compositestructures shown in FIG. 3 can be obtained.

In the process for producing conductive polymers of the presentinvention, sizes of conductive substrates used as working electrodes arenot specifically limited and large sized conductive substrates may beused such as metal meshes with not less than 50 mm×50 mm and coiledspring-shaped members made of metals whose outer diameters are not lessthan 3 mm, or small sized conductive substrates may also be used such ascoiled spring-shaped members made of metals and the like whose diameteris several dozen μm.

A process for producing conductive polymers of the present invention isa process for producing conductive polymer composite structures whichcan preferably be used particularly as easily obtaining conductivepolymer composite structures available as large sized actuator elementsor small-sized actuator elements. In obtaining small sized actuatorelements, it is difficult to process conductive polymer films obtainedby electrochemical polymerization into actuator elements whose outerdiameters or width are less than 1 mm, particularly actuator elementswhose diameters are less than 500 μm and it is further difficult toprocess into cylindrical actuator elements whose outer diameters orwidth are several dozen μm or less than 100 μm, since conductive polymerfilms by themselves do not have sufficient mechanical strength duringprocess. However, in the process for producing conductive polymers ofthe present invention, by selecting conductive substrates beforehand andby conducting the process for producing conductive polymers of thepresent invention, actuator elements can be obtained which are driven toexpand and contract or bend by electrochemomechanical deformation ofconductive polymers with outer diameters or width of less than 1 mmwithout any process in order to obtain desired sizes and shapes ofactuator elements in the obtained conductive polymer compositestructures.

In addition, regarding large-sized elements as well, when conductivepolymers are electrochemically polymerized using large-sized conductivesubstrates for working electrodes in the process for producingconductive polymers of the present invention, conductive polymercomposite structures which can be used as large-sized actuator elementscan easily be obtained.

(Condition for Electrochemical Polymerization)

As methods of electrochemical polymerization used in the process ofproducing conductive polymers, it is possible to use publicly knownmethods of electrochemical polymerization as electrochemicalpolymerization of monomers of conductive polymers. Therefore, publiclyknown electrolytic solution and monomers of conductive polymers can beused and any one of constant potential methods, constant currentmethods, and potential sweep methods can be used for example, saidelectrochemical polymerization is preferably conducted under thecondition where the current density is 0.01 to 20 mA/cm² and reactiontemperature is −70 to 80° C., preferably current density of 0.1 to 2mA/cm² and reaction temperature of −40 to 40° C., and more preferably,reaction temperature of −20 to 30° C.

In the process for producing conductive polymers of the presentinvention, although publicly known solvent can be used as electrolyticsolution for electrochemical polymerization, electrolytic solution whichincludes organic compounds as solvents can be used. It is preferablethat said organic compounds include (1) chemical bonding selected atleast one from the groups of chemical bond made up of ether bond, esterbond, carbon-halogen and carbonate bond and/or (2) functional groupsselected at least one from the groups of functional groups made up ofhydroxyl groups, nitro groups, sulfone groups, and nitryl groups inmolecules.

In addition, publicly known dopant may be included in said electrolyticsolution and in order to obtain larger deformation ratio per redoxcycle, it is preferable to include trifluoromethanesulfonate ion and/oranions including plural of fluorine atoms bonding to a central atom.Further, in order to make deformation ratio per redox cycle of obtainedconductive polymers not less than 16%, as anions in said electrolyticsolution, it is preferable to use perfluoroalkylsulfonylimide ionrepresented by chemical formula (1) instead of usingtrifluoromethanesulfonate ion and/or anions including plural of fluorineatoms bonding to a central atom.(C_(n)F_((2n+1))SO₂)(C_(m)F_((2m+1))SO₂)N⁻  (1)

(Here, n and m are arbitrary integers.)

In the process for producing conductive polymers of the presentinvention, monomers of conductive polymers included in electrolyticsolution for electrochemical polymerization are not specifically limitedas long as they are compounds which become polymers by oxidation byelectrochemical polymerization and show conductivity, and examplesinclude five-membered heterocyclic compounds such as pyrrole, thiophene,isothianaphthene and the like and derivatives of alkyl groups, oxyalkylgroups thereof arid the like. Among them, hetero five-membered ringcompounds such as pyrrole, thiophene and the like or derivatives thereofare preferable and particularly, conductive polymers including pyrroleand/or pyrrole derivatives are preferable for easy production processand stability as conductive polymers. In addition, the above monomerscan be used together in combinations of two or more of them.

(Process for Producing Conductive Polymer Composite Structures)

In the process for producing said conductive polymers as above, saidconductive polymer composite structures can easily be produced. Inparticular, it is preferable to use the following process for producingsaid conductive polymer composite structures. That is, the presentinvention also relates to a process for producing conductive polymercomposite structures comprising the steps of impregnating electrodeholders in an electrolytic bath in electrolytic solution, followed byturning on electricity interposing electrolytic solution between acounter electrode and a working electrode and electrochemicallypolymerizing, thereby obtaining structures in which conductive polymersand conductive substrates are complexed, wherein said holders of workingelectrodes are provided with working electrodes, a terminal portion ofworking electrodes and electrode holder portions, and said workingelectrodes are attached to said terminal portion of working electrodesand said working electrodes include at least coiled conductivesubstrates. In said producing process, electrochemical polymerizationcan be conducted by positioning counter electrodes in the vicinity ofworking electrodes. FIG. 10 is an elevation view of electrode holders 24in the present invention. Electrode holders 24 are provided with aterminal portion of working electrodes 25 and working electrodes 27 areconnected to a terminal portion of working electrodes 25 interposingconnection lines 28 in connecting portion 26 of working electrodes.

Ni plates with longer sideways are used as a terminal portion of workingelectrodes 25. In the process for producing conductive polymer compositestructures of the present invention, shapes of a terminal portion ofworking electrodes are not specifically limited and they may becylindrical, meshed, and the like. In addition, materials of saidterminal portion of working electrodes are not specifically limited aslong as they show conductivity and as long as said working electrodescan be set and conductive materials such as metals and non-metals can beused.

In FIG. 10, ten working electrodes are attached to a terminal portion ofworking electrodes and a working electrode 4 is bundled to form one bytwisting four coiled conductive substrates, and plural of workingelectrodes 27 are positioned in a terminal portion of working electrodes25, thereby forming a group of working electrodes. When many of saidconductive substrates are bundled to form a bundle, electrochemicalpolymerization may be conducted with one working electrode and comparedwith when each of many conductive substrates are subject toelectrochemical polymerization separately followed by bundling with oneelectrochemical polymerization process, time can greatly be reduced. Inaddition, when large-sized actuator elements are to be obtained usingconductive polymer composite structures, it is preferable that many ofworking electrodes are attached to a terminal portion of workingelectrodes using plural of composites with many coiled conductivesubstrates bundled for effective process with less time.

It is preferable that said conductive substrates show conductivity ofnot less than 1.0×10³ S/cm and they may be formed by conductivematerials such as conductive metals, carbon and the like and the surfaceof them may be coated with conductive materials such as conductivemetals, carbon and the like by plating and the like. With theconductivity of not less than 1.0×10³ S/cm as said conductivesubstrates, even when conductive polymer composite structures withenlarged size in the length direction or height direction are used,sufficient potential for displacement such as expansion and contract canbe applied to the whole element. As conductive substrates which includeconductive metals, metal such as Ag, Ni, Ti, Au, Pt, Ta, W, and the likeor alloys thereof, and other alloys such as SUS and the like can beused. In particular, it is preferable that said conductive substratesare W alloys and Ni alloys in order to obtain conductive polymers whichoperate stably in operational electrolytic solution.

In the process for producing conductive polymer composite structures ofthe present invention, said working electrodes may be one coiledconductive substrate with each working electrode or may be bundles inwhich coiled conductive substrates are bundled. When coiled conductivesubstrates used as said working electrodes are long, resistance becomeslarge since metal wires are narrow and long due to coiled conductivesubstrates which are working electrodes, and as the conductivesubstrates get longer, transmission of potential gets worse andformation of conductive polymers on conductive substrates becomesdifficult. In such cases, by making said working electrodes bundles inwhich coiled conductive substrates are bundled, at the time ofelectrochemical polymerization, stable potential can be provided to thewhole conductive substrates and the efficiency of electrochemicalpolymerization improves and time for producing process can be shortened.In addition, since conductive polymer composite structures obtained byelectrochemical polymerization using said bundles are in the state whereplural of conductive substrates are complexed with conductive polymersin which plural of conductive substrates are bundled together, comparedwith the process for obtaining conductive polymer composite structuresby complexing each of coiled conductive substrates separately, the spaceof an electrolyte bath can be saved and the same effect can be obtainedwhen many conductive substrates are complexed at once.

In addition, forms of said bundles used as working electrodes are notlimited as long as the forms have structures in which motion at the timeof expansion and contraction is not inhibited with upward and downwardof plural coils of conductive substrates connected to so that plural ofcoiled conductive substrates contact with each other to make potentialsubstantially constant. For example, forms of said bundles can beselected from bundling coiled conductive substrates like an expander,tubular structures in which coiled conductive substrates are arrangedlike cylinders, bundling coiled conductive substrates by twisting andthe like, depending on how conductive polymer composite structures areused.

Although said bundles are not specifically limited, it is preferablethat said bundles are bundles composed of four to one hundred coiledconductive substrates for good workability and efficiency ofelectrochemical polymerization and such bundles do not inhibitdeformation property of conductive polymer composite structures.

When a bundle with over one hundred coiled conductive substrates isused, electrochemical polymerization to coils inside of the bundle isnot conducted efficiently. However, when electrolytic solution and coilscan contact efficiently with appropriate spaces provided, a bundle withover one hundred coiled conductive substrates can be used.

In FIG. 10, in working electrode 27, connection wire 28 is connected toworking electrode terminal portion 25 at working electrode connectionportion 26 by soldering in which connection wire 28 is connected to theupper part of working electrode 27 when the lengthwise direction forsaid electrode 27 is arranged in the vertical direction. In the processfor producing conductive polymer composite structures of the presentinvention, methods of fixing said connection portion of a workingelectrode are not specifically limited as long as electric conductivityis available by said methods and such methods may be selected fromsoldering, conductive adhesion, spot welding, clip-on, or screwfastening in which connection wires are fixed by screw heads. Forinformation, said connection wires need not be requisite ones and saidworking electrodes may be directly connected to a terminal portion ofworking electrodes and it is preferable that the electrode holders ofthe present invention are provided with conductive connection wires madeof metals in order to facilitate the operation of attaching workingelectrodes to a terminal portion of working electrodes.

In FIG. 10, electrode holders 24 are provided with plate-like electrodefixing portions 29 a, 29 b, 29 c, and 29 d whose thickness issubstantially the same and said electrode fixing portions formframe-like shapes. On back surfaces of electrode fixing portions 29 a,29 b, 29 c, and 29 d combined in frame-like shapes, counter electrodes30 with substantially the same size with frame-shaped outer size formedby said electrode fixing portions are fixed. Sine working electrodeterminal portions 25 are provided on a face of electrode fixing portion29 a and counter electrodes are fixed on back surfaces of electrodefixing portions, the spaces between counter electrodes in each workingelectrode become substantially the game and the amount of conductivepolymer included in each of obtained conductive polymer compositestructures can easily be made substantially constant.

Although the spaces between counter electrodes in each working electrodeare not specifically limited as long as conductive polymer can be formedon working electrodes by electrochemical polymerization, the spaces arepreferably 1 to 50 mm. When the space between a working electrode and acounter electrode is less than 1 mm, short circuit is liable to occur bythe contact of working electrodes and electrodes, and on the other hand,when the space between a working electrode and a counter electrode islarger than 50 mm, voltage becomes too much with constant currentmethods causing electrolytes to deteriorate, causing performance ofgenerated conductive polymers to lower, and with constant potentialmethods, electrolytic current becomes extremely small and it takes timeto form desired amount of conductive polymers in on working electrodes.Further, in the process for producing conductive polymer compositestructures of the present invention, counter electrodes need not alwaysbe fixed to holders of working electrodes Holders of working electrodesmay be fixed in the specified position of an electrolytic bath so thatthe spaces between counter electrodes in each working electrode withsaid counter electrodes fixed to an electrolytic bath.

In FIG. 10, electrode holders are provided with four electrode fixingportions, however, they are not always plural and any shapes such asall-in one frame shapes may be used so long as they do not block offbetween counter electrodes and working electrodes. For example,electrode fixing portions having small areas can be obtained andtherefore, resource saving is available by providing working electrodeterminal portions on plate-shaped electrode fixing portions with longside ways and by fixing them on a specific position of the upper part ofan electrolyte bath so that the working electrodes connected to workingelectrode terminal portions hang vertically downward when counterelectrodes are fixed to an electrolytic bath. Further, it is preferablethat said electrode fixing portions are formed by insulating materialsin order to avoid direct conductivity of counter electrodes and workingelectrodes and although they may be plastics, ceramics, glasses, andinsulating coating metals and the like, polypropylene, PTFE,polyethylene, and glass are more preferably used as easy formation andfor good resistance to solvents. In addition, when 6 said electrodefixing portions do not have insulating property, by sandwiching aninsulating sheet between working electrode terminal portions andelectrode fixing portions or between electrode fixing portions andcounter electrodes, direct conductivity of counter electrodes andworking electrodes can be avoided.

In the process for producing conductive polymer composite structures ofthe present invention, the shapes of counter electrodes are notspecifically limited as long as conductivity is available betweencounter electrodes and working electrodes and shapes may beplate-shaped, meshed, coiled, bar-shaped, cylindrical, and the like. Inaddition, said counter electrodes are not specifically limited as longas they have conductive property and metals such as Ni, Au, Pt, and thelike or carbon may be included.

FIG. 1l shows the state in which a lead for turning on electricity onelectrode holders between counter electrodes and working electrodes inthe process for producing conductive polymer composite structures of thepresent invention. Three leads 31 are connected to working electrodeterminal portion 25 provided in electrode holders 24 and interposinglead 31′, they are connected to power supply 32. Further, leads 10 arealso connected to counter electrode 7 and they are also connected topower supply 9. Suspended, electrode holders 24 are impregnated in anelectrolytic bath 34 provided with electrolytic solution 35 andelectrochemical polymerization is conducted with potential applied bypower supply 32. For information, methods for retaining the state ofimpregnating electrode holders 24 in an electrolytic bath 34 are notspecifically limited, and other than methods of suspending electrodeholders, methods include inserting electrode holders in an electrolytebath providing slots, leaving electrode holders in a form ofself-standing state such as containing them in a box in an electrolytebath and the like and various methods can be used which will fit theshapes and sizes of an electrolyte bath. Further, when electrode holdersare immersed in an electrolyte bath, it is preferable that wholeelectrode holders are immersed in an electrolytic solution exceptworking electrode terminal portions so that conductive polymers are notgenerated on working electrode terminal portions.

In FIG. 11, although leads 31 are connected to working electrodeterminal portions 25 in which the space between connecting portions ofthree leads 31 and working electrode terminal portions 25 are equal sothat constant potential can be applied to each portion of the wholeworking electrode terminal portions 25 which are Ni metal plates, thenumber of leads which are connected to working electrode terminalportions are not specifically limited in the process for producingconductive polymer composite structures of the present invention.

It is preferable that leads which are connected to said workingelectrode terminal portions are connected to working electrode terminalportions in required numbers so that stable potential could be providedto the whole working electrode terminal portions depending on materialsof working electrode terminal portions. In the process for producingconductive polymer composite structures of the present invention,conductive polymers are generated on plural of working electrodesprovided in electrode holders by conducting electrochemicalpolymerization comprising the steps of impregnating electrode holders inan electrolytic solution, followed by turning on electricity interposingelectrolyte between counter electrodes and working electrodes.

(Electrochemomechanical Deformation)

Although in conductive polymer composite structures, supportingelectrolytes for electrochemomechanical deformation are not specificallylimited, it is preferable that said electrolytic solution includescompounds selected at least one from the group oftrifluoromethanesulfonate ion, anions including plural of fluorine atomswhich bond to central atom and sulfonate with a carbon number of notgreater than 3 as supporting electrolytes. The reason is that by makingcompounds selected at least one from the group oftrifluoromethanesulfonate ion, anions including plural of fluorine atomswhich bond to central atom, and sulfonate with a carbon number of notgreater than 3 as supporting electrolytes, further largeelectrochemomechanical deformation per redox can be obtained.

Trifluoromethanesulfonate ion included in electrolytic solution forexpanding and contracting said conductive polymer composite structuresas operational electrolytic solution is a compound represented by thechemical formula of CF₃SO₃ ⁻. Further, anions which include plural offluorine atoms which bond to central atom is the ion having structuresin which plural of fluorine atoms bond to central atom such as boron,phosphorus, antimony, arsenic, and the like. In addition, sulfonate witha carbon number of not greater than 3 are not specifically limited aslong as they are salts of sulfonic acid with a carbon number of notgreater than 3 and for example, sodium methanesulfonate and sodiumethanesulfonate can be used. Said electrolytic solution may be aqueoussolution which includes sodium chloride as supporting electrolytes. Bymainly including sodium chloride which is an electrolyte contained inorganism, in said electrolytic solution, motion is available in whichcompatibility between body fluid in organism and said electrolyticsolution can easily be made. In addition, regarding, method ofelectrochemomechanical deformation, electrolytic solution which operatesconductive polymers may include(C_(n)F_((2n+1))SO₂)(C_(m)F_((2m+1))SO₂)N⁻

(Here, n and m are arbitrary integers) as operational electrolyticsolution.

It is preferable that conductive polymer composite structures whichinclude conductive polymers obtained by the process for producingconductive polymers by using electrochemical polymerization, whereinsaid electrochemical polymerization method uses electrolytic solutionwhich includes perfluoroalkylsulfonylimide ion represented by a chemicalformula of(C_(n)F_((2n+1))SO₂)(C_(m)F_((2m+1))SO₂)N⁻

(Here, n and m are arbitrary integers) are subject toelectrochemomechanical deformation with electrolytic solution whichincludes(C_(n)F_((2n+1))SO₂)(C_(m)F_((2m+1))SO₂)N⁻

(Here, n and m are arbitrary integers) as an operational electrolyte.

Since said conductive polymer composite structures have the structure inwhich said perfluoroalkylsulfonylimide is included in operationalelectrolytic solution, said perfluoroalkylsulfonylimide is easily takenin at the time of expansion of conductive polymer forms inelectrochemomechanical deformation, compared with methods ofelectrochemomechanical deformation which use electrolytes includingtrifluoromethanesulfonate ion, excellent deformation ratio per redox isshown and further, excellent displacement ratio per specific time isshown.

(Use)

Conductive polymer composite structures and stacked layers of thepresent invention can preferably be used as actuators since they cangenerate displacement as mentioned above. In conductive polymercomposite structures of the present invention, for example, when theyare not coated with resins and the like, they can be used as actuatorelements which can be displaced in a linear manner in electrolyticsolution. Stacked layers of the present invention, for example, can beused as actuator elements which are displaced in a linear manner when,for example, either one or both of the upper layer and the lower layerin which conductive polymer containing layers are intermediate layersare solid electrolyte layers having the same or greater deformationproperty at the time of electrochemomechanical deformation of conductivepolymer containing layers. Stacked layers of the present invention, forexample, can be used as actuator elements which are displaced such asbending when, for example, either one of the upper layer and the lowerlayer in which conductive polymer containing layers are intermediatelayers are solid electrolyte layers or resin layers having smallerdeformation property than deformation property at the time ofelectrochemomechanical deformation of conductive polymer containinglayers since solid electrolyte layers or resin layers do not expand orcontract greater than conductive polymer layers do. Actuator elementswhich generate rectilinear displacement or bending displacement can beused as driving parts which generate linear driving force or drivingparts which generate driving force for shifting orbital tracks composedof circular arc portions. Further, said actuator elements can also beused as pressing parts which move in a linear manner.

In other words, said actuator elements can preferably be used as drivingparts which generate rectilinear driving force, as driving parts whichgenerate driving force for moving on track shaped rails composed ofcircular arc portions, or as pressing parts moving in a rectilinearmanner or in a curved manner in OA apparatuses, antennae, seatingdevices such as beds or chairs and the like, medical apparatuses,engines, optical equipments, fixtures, side trimmers, vehicles,elevating machines, food processing devices, cleaning devices, measuringinstruments, testing devices, controlling devices, machine tools,process machinery, electronics devices, electronic microscopes, electricrazors, electric tooth brushes, manipulators, masts, play game devices,amusement devices, simulation devices for automobiles, holding devicesfor vehicle occupants, and expanding devices for accessories inaircraft. Said actuators can be used as driving parts which generaterectilinear driving force, as driving parts which generate driving forcefor moving on track shaped rails composed of circular arc portions, oras pressing parts moving in a rectilinear manner in, for example,valves, brakes, and lock devices used as machinery as a whole includingthe above mentioned instruments such as OA apparatus, measuringinstruments, and the like. Further, other than said devices,instruments, and machines, in mechanical components as a whole, saidactuators can preferably be used as driving parts of positioningdevices, driving parts of posture control devices, driving parts ofelevating devices, driving parts of carriers, driving parts of movingdevices, driving parts of regulating devices for the content amount,directions, or the like, driving parts of adjusting devices of axes andthe like, driving parts of guiding devices, and as pressing parts ofpressing devices. In addition, said actuators, as driving parts in jointdevices, can preferably be used as driving parts which impart revolvingmovement to joint portions or joints where direct driving is applicablesuch as joint intermediate members and the like. Said actuator elementsof the present invention can preferably be used as driving parts ofchangeover devices for wires and the like, driving parts of reversinggears for products and the like, driving parts of winding devices forwires and the like, driving parts of traction apparatuses, and drivingparts of swing devices in horizontal directions such as oscillation andthe like.

Said actuator elements of the present invention can preferably be used,for example, as driving parts of ink jet parts in ink jet printers suchas printers for CAD and the like, driving parts for displacing thedirection of optical axis of said optical beam in the printer, headdriving parts of disc drive devices such as external storage devices andthe like, and as driving parts of pressing contact force regulatingmeans of paper in feeders of image forming devices which includeprinters, copying machines, and facsimiles.

Said actuator elements of the present invention can preferably be used,for example, as driving parts of a drive mechanism relocating measuringportions or feeding portions making high frequency power feeding portionsuch as antennae shared between the frequencies for radio astronomy moveto second focul point, and driving parts for lifting mechanism in mastsused for example for vehicle-loaded pneumatic operating stretchablemasts (telescoping masts) and the like or antennae.

Said actuator elements of the present invention can preferably be used,for example, as driving parts of massaging parts of chair-shapedmassagers, to driving parts of nursing beds or medical beds, drivingparts of posture control devices of electrically reclining chairs,driving parts of stretching rods controlling sitting up and downmovement of backrest and ottoman of reclining chairs used, as massager,comfort chairs and the like, driving parts used as backrests forreclining chairs in nursing beds or leg rests in furniture on whichpeople place some body portions or driving parts used as rotation driveand the like of nursing beds, and driving parts for controlling postureof uprising chairs.

Said actuator elements of the present invention can preferably be used,for example, as driving parts of testing devices, driving parts ofpressure measuring devices for blood pressure and the like used asexternal blood treatment apparatus, driving parts for catheters,endoscopes, device or something, tweezers, and the like, driving partsof cataract operation devices using ultrasonic, driving parts ofmovement devices such as jaw movement devices and the like, drivingparts of means for relatively deforming members of chassis of hoists forsickly weak people, and driving parts for elevation, moving, posturecontrol, and the like of nursing beds.

The actuators of the present invention can preferably be used as, forexample, driving parts of vibration-control devices for decreasingvibration transmitted from vibration generating parts such as enginesand the like to vibration receivers such as frames and thee like,driving parts of valve train devices for intake and exhaust valves ofinternal combustion engine, driving parts of fuel-control devices ofengines, and driving parts of fuel-providing systems of engines such asdiesel engines, and the like.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts of calibration devices of imaging deviceswith compensation function for blurring of images due to hand movement,driving parts of lens driving mechanism of lens for home video camera,and the like, driving parts of driving mechanism of mobile lenses ofoptical devices such as still cameras, video cameras, and the like,driving parts of automatic focus parts of cameras, driving parts oflens-barrel used as image-taking devices of cameras, video cameras, andthe like, driving parts of automatic guiders which take in the light ofoptical telescopes, driving parts of lens driving mechanism orlens-barrel of optical devices having two optical systems such asstereoscopic cameras, binoculars, and the like, driving parts orpressing parts providing compressing force to fibers of wavelengthconversion of fiber-type wavelength tunable filters used as opticalcommunication, optical information processing and for optical measuringand the like, driving parts of optical as alignment devices, and drivingparts of shutter mechanism of cameras.

Said actuator elements of the present invention can preferably be usedas, for example, pressing parts of fixtures for caulking hose clips tohose bodies.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts of coil springs and the like ofautomobile suspensions, driving parts of fuel filler lid openers whichunlock fuel filler lid of vehicles, driving parts of stretching andretraction of bulldozer blades, driving parts of driving devices forchanging gear ratios of automotive transmissions automatically, or fordisengaging and engaging clutches automatically.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts of elevating devices of wheel chairs withseat plate elevation devices, driving parts of elevation devices foreliminating the level difference, driving parts of elevation transferequipment, driving parts for elevating medical beds, electric beds,electric tables, electric chairs, nursing beds, elevation tables, CTscanners, cabin tilt devices for trucks, lifters, and the like, eachkind of elevation machine devices and driving parts of loading andunloading devices of special vehicles for carrying heavy materials.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts of discharge amount controlling mechanismsuch as nozzle devices for food discharge used in food processingdevices, and the like.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts for elevating and the like of a carriageof cleaning devices, cleaning parts and the like.

The actuators of the present invention can preferably be used as, forexample, driving parts of measuring parts of three dimensional measuringdevices measuring surface shape, driving parts of stage devices, drivingparts of sensor parts of such systems as detecting operatingcharacteristics of tires, driving parts of initial speed-impartingdevices of evaluation equipment of impact response of force sensors,driving parts of piston driving devices of piston cylinders of devicesfor testing water-permeability hole, driving parts for aiming in thedirection of elevation angles in condensing and tracking type powergenerating equipments, driving parts of vibrating devices of tuningmirrors of sapphire laser oscillation wavelength switching mechanism formeasuring devices which include measuring devices for gas concentration,driving parts of XYθ table when alignment is required in testing devicesof printed circuit boards or in testing devices of flat panel displayssuch as liquid crystals, PDPs and the like, driving parts of adjustableaperture devices used in charged particles beam systems and the likesuch as electronic beam (E beam) systems, focused ion beam (FIB)systems, and the like, driving parts of supporting devices of elementsunder test or sensing parts in flatness measuring devices, and drivingparts of precisely positioning devices such as microscopic deviceassembly, semiconductor photolithography machines, semi-conductorinspecting devices, three dimensional measuring devices, and the like.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts of electric razors and driving parts ofelectric toothbrushes.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts of imaging devices of three dimensionalobjects, driving parts of optical devices for optical system adjustingfocal depth for reading out commonly used as CDs and DVDs, driving partsof variable mirrors capable of easily varying focal positions bychanging the shape of a surface subject to drive by plural of actuatorsas active curved surfaces to approximately form a desirable curvedsurface, driving parts of disc devices capable of moving move units in arectilinear manner having at least one magnetic head such as opticalpick up devices and the like, driving parts of head load mechanisms ofmagnetic tape head actuator assembly such as linear tape storage systemsand the like, driving parts of image-forming devices applied forelectronograph copying machines, printers, facsimiles, and the like,driving parts of loaded members such as magnetic head members, and thelike, driving parts of optical disc exposure devices which drive andcontrol focusing lens groups in the direction of optical axis, drivingparts of head driving means which drive optical heads, driving parts ofinformation recording and reproducing devices which record informationon record media or play information recorded on record media, anddriving parts for switching operations of circuit breaker (circuitbreaker for power distribution).

Said actuator elements of the present invention can preferably be usedas driving parts of the following devices, for example, driving parts ofpress molding and vulcanizing devices for rubber compositions, drivingparts of parts arrangement devices which arrange delivered parts insingle rows or in single layers, or arrange said parts in desiredposture, driving parts of compression molding devices, driving parts ofholding mechanism of welding devices, driving parts of bag filing andpackaging machines, driving parts of machine tools such as machiningcenters and the like, molding machines such as injection moldingmachines, press machines, and the like, driving parts of fluid coatingdevices such as printing devices, coating devices, lacquer sprayingdevices, and the like, driving parts of manufacturing devices whichmanufacture camshafts and the like, driving parts of hoisting devices ofcovering materials, driving parts of selvedge control elements and thelike in shuttle-less looms, driving parts of needle drive systems oftufting machines, looper driving systems, knife driving systems, and thelike, driving parts of cam grinders or polishing devices which polishparts such as ultra precision machining tools, driving parts of breakdevices of harness frames of looms, driving parts of opening deviceswhich form opening portions of warp threads for weft thread insert inlooms, driving parts of peeling devices of protection sheets ofsemiconductor substrates and the like, driving parts of threader&,driving parts of assembly devices of electron guns for CRT, drivingparts of linear control devices with shifter fork drive selection ofTorchon lace machines for manufacturing Torchon lace having applied usesfor welt for clothes, table cloths, sheet coverings, and the like,driving parts of horizontal moving mechanisms of anneal window drivingdevices, driving parts of support arms of glass melting kiln forehearth,driving parts of making forward and backward movement for rack ofexposure devices of fluorescent screen forming methods of color TV tubesand the like, driving parts of torch arms of ball bonding devices,driving parts of bonding heads in XY directions, driving parts ofmounting processes of parts or measuring inspection processes of partsin mounting chip parts or measuring using probes, elevation drivingparts of cleaning supports of board cleaning devices, driving parts ofmaking probe heads scanning on glass board forward or backward, drivingparts of positioning devices of exposure devices which transcribepatterns on boards, driving parts of microscopic positioning deviceswith sub micron orders in the field of high precision processes, drivingparts of positioning devices of measurement devices of chemicalmechanical polishing tools, driving parts for positioning stage devicespreferable for exposure devices or scanning exposure devices used at thetime of manufacturing circuit devices such as conductor circuitelements, liquid crystal display elements, and the like in lithographyprocesses, driving parts of means of carrying works and the like orpositioning works and the like, driving parts for positioning orcarrying such as reticle stages or wafer stages and the like, drivingparts of stage devices for precisely positioning in chambers, drivingparts of positioning devices of work pieces or semi-conductor wafers inchemical mechanical polishing systems, driving parts of stepper devicesof semi-conductors, driving parts of devices precisely positioning inguiding stations of processing machines, driving parts ofvibration-control devices of passive vibration-control and activevibration-control types for each kind of machine represented by machinetools and the like such as NC machines, machining centers, and the like,or steppers in IC industry, driving parts of displacing reference gridsboard of light beam scanning devices in the direction of optical axis ofsaid light beam in exposure devices used as lithography process formanufacturing semi-conductor elements or liquid crystal display elementsand the like, and driving parts of transfer devices transferring intoitem processing units in the traverse direction of conveyors.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts of positioning devices of probes ofscanning probe microscopes such as electron microscopes and the like,and driving parts of positioning and the like of micro-motion devicesfor sample in electron microscopes.

Said actuator elements of the present invention preferably be used as,for example, driving parts of joint mechanisms represented by wrists andthe like of robot arms in robots including auto welding robots,industrial robots, robots for nursing care or manipulators, drivingparts of joint other than direct drive type, fingers of robots, drivingparts of motion converting mechanisms of slide retractable zipperdevices used for fingers of robots, hands of robots and the like,driving parts of micro manipulators for operating microscopic objects inany state in cell minute operations or in assembly operation ofmicroscopic parts and the like, driving parts of artificial limbs suchas electric artificial arms and the like having plural of fingers whichcan freely open and close, driving parts of robots for handling, drivingparts of assistive devices, and driving parts of power suits.

Said actuator elements of the present invention can preferably be usedas, for example, pressing parts of the devices pressing upper rotaryblades, lower rotary blades, or the like of side trimmers.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts of generators and the like in playdevices such as for pachinko games and the like, driving parts ofamusement devices such as dolls, pet robots, and the like, and drivingparts of simulation devices of those for automobiles.

Said actuator elements of the present invention can preferably be usedas, for example, driving parts of valves used as machines in generalincluding the above instruments and the like, and for example, saidactuators can preferably be used as driving parts of valves ofre-condensers of vaporized helium gas, driving parts of bellows typepressure sensitive control valves, driving parts of opening deviceswhich drive harness frames, driving parts of vacuum gate valves, drivingparts of control valves of solenoid operations for liquid pressuresystems, driving parts of valves with movement transmitting devicesusing pivot levers built in, driving parts of valves of movable nozzlesof rockets, driving parts of suck back valves, and driving parts ofregulator valves.

Said actuator elements of the present invention can preferably be usedas, for example, pressuring parts of brakes used as machines in generalincluding the above mentioned instruments and the like, and for example,pressuring parts of control devices which are preferably used as brakesfor emergency, security, stationary, and the like, and pressuring partsof brake structures and brake systems.

Said actuator elements of the present invention can preferably be usedas, for example, pressuring parts of lock devices used as machines ingeneral including the above mentioned instruments and the like and forexample pressuring parts of mechanical lock devices, pressuring parts ofsteering lock devices for vehicles, pressuring parts of powertransmission devices which have both load shedding mechanisms andconnection releasing mechanisms.

Said actuator elements of the present invention can preferably be usedas, for example, pressuring parts of brakes used as machines in generalincluding the above mentioned instruments, and pressuring parts ofcontrol devices which are preferably used as brakes for emergency,security, stationary, and the like, and pressuring parts of brakestructures and brake systems.

Said actuator elements of the present invention can preferably be usedas, for example, pressuring parts of lock devices used as machines ingeneral including the above mentioned instruments and the like and forexample, pressuring parts of mechanical lock devices, pressuring partsof steering lock devices for vehicles, pressuring parts of powertransmission devices which have both load shedding mechanisms andconnection releasing mechanisms.

Since said actuator elements are light weighted, are composed of simpledevice structures, and are less likely to generate displacementdisadvantageous to press motion such as buckling and the like andfurther, since said actuators can easily generate pressing force, theycan preferably be used as pressuring parts of audio-visual devices,tactile devices, pressing devices, gripping devices, push-out devices,bending devices, clamping devices, adhesion devices, or contact devices.

Said actuator elements of the present invention can preferably be usedas pressing parts of the following devices; audio-visual devices ortactile devices for visually or aurally handicapped persons in whichpress parts form Braille, pressing parts of flexible variableendoscopes, pressing parts of front fork for two-wheeled vehicle,pressing parts which shuts off opening portions of high-frequency waveorifice passage in pneumatic controlling fluid enclosing type vibrationproofing device, pressing parts for pressing valve axis end portions invalve resting device for cylinder control type engines, pressing partswhich press contacts plate members in injection molding devices intodies, pressing parts which pressurizes image elements towards said lensseats in image devices such as television cameras, video cameras,digital cameras, and the like, pressing parts which unlock retention ofrecording medium by pressing chuck claws in information reproducingmechanism provided with clamping mechanism, pressing parts for biasapplication (including ground) for allowing conductivity to conductivesubstrates locally in electrolytic driven image displaying medium,pressing parts which drives and presses in the propulsive direction inbase pushing devices for shield tunneling methods, pressing parts usedas transporting means in image forming devices, and pressing parts whichpress-contacts filmy polishing members to plate members in polishingdevices in plate members.

Said actuator elements of the present invention can preferably be usedfor the pressing parts of the following devices; pressing parts whichpresses movable spring plates in the direction of contacting fixedcontact in electromagnetic relay, pressing parts of speed reductionmechanism with great speed reduction ratio built in NC machine tools andthe like, pressing parts for molding hollow members with specific shapesby contacting and pressing to stock pipes in processing devices ofhollow products for spinning process, pressing parts for holding bypressing cylindrical articles between the plate type holding members inthe holding device of cylindrical articles and pressing parts, pressingparts for pressing masking plates in leakage testing devices measuringthe amount of leakage of boring holes bored in cylinder blocks and thelike, pressing part for pressing flexible tubes in tube pumps preferablyused as discharging liquid in constant amount little by little, pressingparts for transmitting driving force from the engine to front wheels orrear wheels with distribution ratio depending on specific pressing forceby pressing multi-plate clutches with specific pressing force in drivingforce distributing devices which transmit driving force from the enginesto front wheels and rear wheels with the specific distribution ratio,pressing parts of pusher pressing units in coil inserting devices,pressing parts or separating the end portion of seal parts in releasingdevices of adhesive seal parts from said release paper, pressing partsfor pressurizing said supporting arms by pressing said locking parts indancer roller devices which control transfer tension of sheet materials.

Said actuator elements of the present invention can preferably be usedas pressing parts which can press driven side clutch claws to drivingside clutch claws in planting parts of rice transplanters, pressingparts of fixed platens which presses substantially center portion of hotplates in hot press devices for obtaining laminates, lead pressing partsforming bending portions of a lead in lead forming equipment ofsemi-conductor devices, pressing parts which press detection levers fordetecting the position of disc trays in disc tray position detectingmechanisms, pressing parts making film pressing plates tightly adhere infilm carriers which scan images, and pressing parts which operate boringaugers for boring new strainer holes on a pipe wall in constructiondevices of function regeneration method of underground water collectingand draining pipes.

In addition, other than for the use of pressing parts of the abovedevices, actuator elements can be used as shatter positioning devices,boring work devices, provided with boring bars, laser welding devices,apparatus for extruding fish paste products, video tape cassettes,transmission devices for industrial vehicles, tabular body end partfixing devices, patting apparatus for reinforcing materials andrepairing materials of concrete structures, folding and laminatingdevices of sheets, paper delivery devices, driving devices of movingobjects, printers, electric circuit cut off devices, heating deviceswith temperature detecting unit, liquid crystal display devices, imageforming devices, recorders, bread slicers, tools for two-shaftconcurrent fastening, powder molding devices, paper sheet handlers,fixing devices of seamless belts, optical fiber connecting devices,shatter mechanisms of vacuum press devices, image blur correctingdevices, image scanning devices, medium housing mechanisms, labeladhering devices, stencil printing devices, press processing devices,deburring devices for outer periphery of the work, disc devices, cuttermounting structures, prize-winning devices for game machines, apparatusfor loading wafer carrier containers, molds for partially bondinginterior trim, drawing frames, clamp devices, measuring apparatus, heattreating furnaces, oil pumps, bending devices, motor with positionswitch, carrying devices for partition panels, and cam shaft materialsupporting devices.

EXAMPLES

Hereinafter, Examples and Comparative Examples are shown, however, thepresent invention is not limited to these Examples and ComparativeExamples.

Example 1

Electrolytic solution was prepared by dissolving pyrrole which is amonomer and a dopant ion salt as shown in Table 1 into medium stated inTable 1 by a publicly known stirring method. This electrolytic solutionhas monomer concentration of 0.25 mol/l and the dopant salt in Table 1is 0.5 mol/l. Conductive polymer composite structures of Example 1having the shapes shown in Table 1 were obtained by using thiselectrolytic solution and by conducting electrochemical polymerizationwith constant current methods with the current density of 0.2 mA/cm² bysetting working electrodes and counter electrodes. As said workingelectrodes, conductive substrates shown in Table 1 (metal mesh, tradename “Au Ami 0.1 mmφ, 100 mesh”, manufactured by Tokuriki Honten Co.,Ltd) were used. As said counter electrodes, commercially available Ptelectrodes were used. In addition, in the tables, “-” shows that therewere no appropriate matters,

Example 2

Conductive polymer composite structures of Example 2 were obtained inthe same way as in Example 1, except that conductive substrates of Table1 (metal mesh, Ni mesh (0.05 mmφ, 200 mesh) manufactured by RareMetallic Co., Ltd.) were used.

Examples 3 to 8

Conductive polymer composite structures of Examples 3 to 8 were obtainedin the same way as in Example 1, except that conductive substrates whichwere coiled spring members of Tables 1 and 2 were used and that thesolvent and dopant salt of Table 1 or 2 were used. In addition, ascoiled spring members used in Example 3, spring members formed as acharacteristic of Table 1 were used by using “Ni wire, wire diameter0.10 mmφ” (manufactured by Rare Metallic Co., Ltd.) and as coiled springmembers used in Example 4, trade name “SUS/Ni plated coil, outerdiameter 0.5 mmφ, wire diameter 40 mmφ, pitch 110 μm” (manufactured byNippon cable system Inc.) were used. As coiled spring members used inExample 5, “Pt/w coil, outer diameter 0.5 mmφ, wire diameter 40 μmφ,pitch 110 μm” (manufactured by Nippon cable system Inc.) were used. Andin Examples 6 and 8, “W coil, outer diameter 0.25 mmφ, wire diameter0.03 mm, pitch 60 μm” (manufactured by Nippon cable system Inc.) wereused. In Example 7, trade name “Inconel X750” was used.

Comparative Examples 1 to 4

Pyrrole which is a monomer and dopant ion salt stated in Tables 1 or 2were dissolved in solvent stated in Tables 1 or 2 by a publicly knownstirring method and an electrolytic solution in which monomerconcentration is 0.25 mol/l and concentration of dopant ion salt inTables 1 or 2 of 0.5 mol/l was prepared. To this electrolytic solution,ITO electrode plates were used as working electrodes. Pt electrodes wereused as counter electrodes, and by conducting electrochemicalpolymerization employing constant current method if polymerizationcurrent density of 0.2 mA/cm², conductive polymers were obtained onworking electrodes. Further, by stripping off obtained conductivepolymers from ITO electrode plates, filmy conductive polymer films wereobtained.

“-” in the Tables shows that there is no appropriate matter. In theTables, DME shows 1,2-dimethoxyethane and TBABF₄ showstetrabutylammonium tetrafluoroborate. Conductivity of conductive polymercomposite structures and of conductive polymer films were measured byusing a conductivity measuring machine (four-probe measuring method,trade name “low-resistivity measuring machine Loresta-GP” manufacturedby Mitsubishi Chemical Corporation) TABLE 1 Comparative Example Example1 2 3 4 5 1 2 conductive substrate material Au Ni Ni SUS/Ni Pt — — plateshape mesh mesh coil coil coil — — opening 100 200 — — — — (mesh) pitch(μm) — — 200 110 110 coil outer — — 3 0.5 0.5 — — diameter wire 0.100.05 0.10 0.04 0.04 — — diameter (mm) conductivity 4 × 10⁵ 3 × 10⁴ 1 ×10⁵ 1 × 10⁴ 1 × 10⁵ — — (S/cm) electrolyte solvent DME DME DME DME DMEDME DME dopant salt TBABF₄ TBABF₄ TBABF₄ TBABF₄ TBABF₄ TBABF₄ TBABF₄element form polymer polymer polymer polymer polymer conductiveconductive composite composite composite composite composite polymerpolymer structures structures structures structures structures film filmshape filmy filmy cylindrical cylindrical cylindrical filmy filmy lengthof 50 50 50 50 50 15 50 elements (mm) conductivity 5 × 10⁴ 5 × 10³ 1 ×10⁸ 1 × 10⁸ 6 × 10⁸ 1 × 10² 1 × 10² (S/cm) deformation propertysupporting NaPF₆ NaPF₆ NaPF₆ NaPF₆ NaPF₆ NaPF₆ NaPF₆ electrolytesuitability ◯ ◯ ⊚ ⊚ ⊚ ⊚ Δ for deformation

TABLE 2 Comparative Example Example 6 7 8 3 4 conductive substratematerial W Incone1 W — — X750 shape coil coil coil — — opening — — — — —(mesh) pitch (μm) 60 60 60 coil outer 0.26 0.25 0.25 — — wire 0.03 0.030.03 — — diameter (mm) conductivity 2 × 10⁵ 1 × 10⁴ 2 × 10⁵ — — (S/cm)electrolyte solvent methyl methyl methyl methyl methyl benzoate benzoatebenzoate benzoate benzoate dopant salt TBABF₄ TBABF₄ TBACF₈ TBABF₄TBABF₄ SO₈ element form polymer polymer polymer conductive conductivecomposite composite composite polymer polymer structure structurestructure film film shape cylindrical cylindrical cylindrical filmyfilmy length of 50 50 50 15 50 elements (mm) conductivity 3 × 10⁴ 1 ×10³ 3 × 10⁸ 1 × 10² 1 × 10³ deformation property supporting NaBF₄ NaBF₄NaBF₄ NaBF₄ NaBF₄ electrolyte suitability ⊚ ⊚ ⊚ ⊚ Δ for deformation

TABLE 3 Comparative Example Example 1 2 1 2 3 4 mechanical 53 111 17 1739 39 strength (MPa)(Evaluation)

(Deformation Property)

Elements with the length stated in Table 1 were obtained usingconductive polymer composite structures of Examples 1 to 8 andconductive polymer films stated in Comparative Examples 1 to 4. Saidelements were held in electrolytic solution by dissolving them in waterto make supporting electrolytes stated in Table 1 be 1 mol/l, therebymeasuring deformation ratio per redox cycle by the method below. Widthof elements obtained from conductive polymer composite structures inExamples 1 and 2 and from conductive polymer films in ComparativeExamples 1 to 4 was set to be 2 mm.

Elements obtained from conductive polymer composite structures inExamples 1 to 8 and elements obtained from conductive polymer films inComparative Examples 1 to 4 were prepared as operational electrodes andoperational electrodes were held in said electrolytic solution.Operational electrodes were prepared out of elements which were obtainedfrom the conductive polymer composite structures of Examples 1 to 8 andfrom the conductive polymer films of Comparative Examples 1 to 4, andthe operational electrodes were held in said electrolyte. Counterelectrodes were prepared out of Pt electrodes and potential was cycled(between −0.9 V and +0.7 V vs. Ag/Ag⁺) by connecting each terminalportion of the electrodes to the power supply interposing a leadtherebetween thereby measuring the electrochemomechanical deformation(change in length). Difference of deformation (electrochemical strain)obtained by expansion and contract of operational electrodes by theapplication of one cycle (per redox cycle) was evaluated based on thefollowing criteria. The results are shown in Tables 1 and 2.

[Evaluation Criteria of Deformation Property]

{circle around (∘)}: Excellent in deformation ratio and excellent indeformation property as actuator elements.

◯: Good in deformation ratio with deformation property practically usedas actuator elements.

Δ: Poor in deformation ratio and not suitable for practical use asactuator elements.

×: No deformation

[Mechanical Strength]

Mechanical strength (tensile strength) of conductive polymer compositestructures in Examples 1 and 2 and conductive polymer film ofComparative Examples 1 to 4 having similar shapes were measured usingtrade name “Digital gauge 9810” (manufactured by AIKOH ENGINEERING CO.,LTD)). The results are shown in Table 3.

[Result]

Elements obtained from conductive polymer composite structures inExamples 1 and 2 were filmy elements longer than that of elements inComparative Example 1 (15 mm) showed deformation property which can bepractically used as actuator elements. On the other hand, in theelements in Comparative Example 2 which are conductive polymer films,although element size of Examples 1 and 2 were the same, they were notpractically used as actuator elements due to poor deformation propertysince conductive substrates were not included. Further, regardingelements of Comparative Example 1, although they showed good deformationproperty and were excellent as actuator elements, since they were smallin size which is conventional, they were not suitable for the use oflarge actuators.

Although elements obtained from conductive polymer composite structuresin Examples 3 to 8 were cylindrical elements longer than that ofComparative Example 1 (15 mm), since it included conductive substrates,they showed excellent deformation property equivalent to deformationproperty of elements in Comparative Example 1 and they were alsoexcellent as actuators.

Conductive polymer composite structures in Examples 1 to 8 haveconductivity of not less than 1×10³ S/cm and compared with theconductivity of conductive polymer film in Comparative Examples 1 and 2,the conductivity is 10 times larger. For this reason, when conductivepolymer composite structures of the present invention are used asactuator elements, actuator elements are capable of imparting potentiallarge enough to make displacement such as expansion and contraction andthe like all over it even when the size thereof is enlarged andtherefore, they are practical enough to be used as actuator for largeuses such as driving parts of robot hands and the like.

Conductive polymer composite structures in Examples 1 and 2 showedexcellent mechanical strength of 53 MPa and 111 MPa. On the other hand,mechanical strength of conductive polymer alms in Comparative Examples 1and 2 was 17 MPa. In conductive polymer composite structures inkExamples 1 and 2, about as 3 times and 7 times as large mechanicalstrength was shown compared with conductive polymer films in ComparativeExamples 1 and 2 with the same shapes (filmy) and the mechanicalstrength was greatly improved.

In addition, regarding Comparative Example 3, when the length ofelements is 15 mm, deformation property is excellent. However, when theelements are elongated using the conductive polymers with the samecomposition as in Comparative Example 3, as shown in Comparative Example4 respectively, deformation characteristics lower. In addition,regarding Comparative Examples 3 and 4, mechanical strength is alsoextremely low compared with that of Comparative Examples 1 and 2 whoseshapes are filmy and therefore similar. Therefore, Examples 1 and 2 haveexcellent deformation property and mechanical strength compared withconductive polymer films shown in Comparative Examples 1 to 4.

In addition, in conductive polymer composite structures of Examples 1 to8, since conductive polymers are formed on surfaces of wire materialswhich compose conductive substrates, by using conductive substrateshaving a thickness, an outer diameter and a width which are thinner bythe thickness of conductive polymers formed on conductive substrates,actuator elements can easily be obtained which are driven to makeexpansion and contraction or bending motion by electrochemomechanicaldeformation of conductive polymers whose outer diameter or width is lessthan 1 mm.

INDUSTRIAL APPLICABILITY

Used for actuator elements, conductive polymer composite structures ofthe present invention are capable of making satisfactory displacementsuch as expansion, contraction, and the like as large sized actuators aswell compared with conventional conductive polymer elements and sincethey can be driven for practical uses, they are preferably used as largesized actuators such as robot hands, artificial muscles and the like. Inparticular, the conductive polymer composite structures of the presentinvention can preferably be used as driving parts of positioningdevices, posture control devices, elevating devices, carrier devices,moving devices, regulating devices, adjusting devices, guiding devices,joint devices, changeover devices, reversing gears, winding devices,traction apparatuses, and swing devices and pressing parts of pressingdevices, pressurizing devices, gripping devices, push-out devices,bending devices, clamping devices, adhesion devices, and contactdevices.

Conductive polymer composite structures of the present invention includeconductive substrates and conductive polymers and when said conductivesubstrates are consecutive structures and are included in almost all ofthe said conductive polymer composite structures, small sized actuatorswith the outer diameter or width of less than 1 mm can be produced,which is hard to be produced when conductive polymers alone are used.Further, said conductive polymer composite structures can produceactuator elements whose diameter is less than 500 μm and smalleractuator elements with dozens micron diameters such as 100 μm can alsobe produced.

In addition, since the process for producing conductive polymers of thepresent invention can easily give conductive polymer compositestructures, it is preferable for process for producing conductivepolymers.

1. Conductive polymer composite structures comprising conductivesubstrates and conductive polymers, wherein said conductive substrateshave deformation property, and conductivity of said conductivesubstrates is not less than 1.0×10³ S/cm.
 2. Layered structurescomprising conductive polymer-containing layers and solid electrolytelayers, wherein said conductive polymer-containing layers are providedwith conductive polymer composite structures which include conductivesubstrates and conductive polymers, said conductive substrates havedeformation property, and conductivity of said conductive substrates isnot less than 1.0×10³ S/cm.
 3. Actuator elements which are driven forexpansion and contraction or bending by electrochemomechanicaldeformation of conductive polymers, wherein an outer diameter or widthof said actuator elements is less than 1 mm.
 4. Bundles of conductivepolymer composite structures provided with not less than two bundles ofconductive polymer composite structures comprising conductive substratesand conductive polymers, wherein said conductive substrates havedeformation property and conductivity of said conductive substrates isnot less than 1.0×10³ S/cm.
 5. Bundles of conductive polymer compositestructures as set forth in claim 4, wherein said conductive substratesare coiled spring members, said conductive polymer composite structuresare cylindrical bodies, and said bundles are bundles of said cylindricalbodies.
 6. A process for producing conductive polymers byelectrochemical polymerization with conductive substrates as workingelectrodes, wherein said conductive substrates have deformation propertyand conductivity of said conductive substrates is not less than 1.0×10³S/cm.
 7. Positioning devices, posture control devices, elevatingdevices, carrier devices, moving devices, regulating devices, adjustingdevices, guiding devices, joint devices, changeover devices, reversinggears, winding devices, traction apparatuses, and swing devices usingconductive polymer composite structures set forth in claim 1 for drivingparts.
 8. Pressing devices, pressurizing devices, gripping devices,push-out devices, bending devices, clamping devices, adhesion devices,and contact devices using conductive polymer composite structures setforth in claim 1 for pressing parts.
 9. Positioning devices, posturecontrol devices, elevating devices, carrier devices, moving devices,regulating devices, adjusting devices, guiding devices, joint devices,changeover devices, reversing gears, winding devices, tractionapparatuses, and swing devices using layered structures set forth inclaim 2 for driving parts.
 10. Pressing devices, pressurizing devices,gripping devices, push-out devices, bending devices, clamping devices,adhesion devices, and contact devices using layered structures set forthin claim 2 for pressing parts.
 11. Process for producing conductivepolymer composite structures comprising conductive polymers andconductive substrates are complexed comprising the steps of immersingelectrode holders in an electrolyte which can be immersed in anelectrolyte bath, followed by electrochemical polymerization by turningon electricity interposing an electrolyte between counter electrodes andworking electrodes, wherein said working electrode holders are providedwith working electrode, working electrode terminal portions andelectrode holder portions, said working electrodes are attached to saidworking electrode terminal portions, and said working electrodes includeat least coiled conductive substrates.
 12. A process for producingconductive polymer composite structures as set forth in claim 11,wherein plural of working electrodes are attached to terminal portionsof said working electrodes.
 13. A process for producing conductivepolymer composite structures as set forth in claim 11, wherein holdersof said working electrodes are further provided with counter electrodes.14. A process for producing conductive polymer composite structures asset forth in claim 13, wherein said counter electrodes are held with aspace of 0.1 to 100 mm between said working electrodes and counterelectrodes.
 15. A process for producing conductive polymer compositestructures as set forth in claim 9, wherein said working electrodescomprise layered structures in which plural of coiled conductivesubstrates are bundled.